Surface modification layer for conductive feature formation

ABSTRACT

Embodiments described herein relate generally to methods for forming a conductive feature in a dielectric layer in semiconductor processing and structures formed thereby. In some embodiments, a structure includes a dielectric layer over a substrate, a surface modification layer, and a conductive feature. The dielectric layer has a sidewall. The surface modification layer is along the sidewall, and the surface modification layer includes phosphorous and carbon. The conductive feature is along the surface modification layer.

PRIORITY CLAIM AND CROSS-REFERENCE

This application is a continuation of U.S. patent application Ser. No.16/145,457, entitled “Surface Modification Layer for Conductive FeatureFormation,” filed on Sep. 28, 2018, which application is incorporatedherein by reference.

BACKGROUND

The semiconductor integrated circuit (IC) industry has experiencedexponential growth. Technological advances in IC materials and designhave produced generations of ICs where each generation has smaller andmore complex circuits than the previous generation. In the course of ICevolution, functional density (e.g., the number of interconnecteddevices per chip area) has generally increased while geometry size(e.g., the smallest component (or line) that can be created using afabrication process) has decreased. This scaling down process generallyprovides benefits by increasing production efficiency and loweringassociated costs. However, scaling down has also led to challenges thatmay not have been presented by previous generations at largergeometries.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIGS. 1 through 6 are cross-sectional views of respective intermediatestructures during an example method for forming a conductive feature inaccordance with some embodiments.

FIGS. 7A, 7B, and 7C are a mechanism for forming a surface modificationlayer in accordance with some embodiments.

DETAILED DESCRIPTION

The following disclosure provides many different embodiments, orexamples, for implementing different features of the provided subjectmatter. Specific examples of components and arrangements are describedbelow to simplify the present disclosure. These are, of course, merelyexamples and are not intended to be limiting. For example, the formationof a first feature over or on a second feature in the description thatfollows may include embodiments in which the first and second featuresare formed in direct contact, and may also include embodiments in whichadditional features may be formed between the first and second features,such that the first and second features may not be in direct contact. Inaddition, the present disclosure may repeat reference numerals and/orletters in the various examples. This repetition is for the purpose ofsimplicity and clarity and does not in itself dictate a relationshipbetween the various embodiments and/or configurations discussed.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The apparatus may be otherwise oriented (rotated 90 degreesor at other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly.

Embodiments described herein relate generally to methods for forming aconductive feature in a dielectric layer in semiconductor processing andstructures formed thereby. In some embodiments, surfaces of thedielectric layer that define an opening in which the conductive featureis formed are treated with a phosphoric acid derivative to form asurface modification layer on those surfaces. The conductive feature isthen formed in the opening and on the surface modification layer. Thesurface modification layer can, among other things, repair damage to thedielectric layer that may be caused by the formation of the openingthrough the dielectric layer. Other advantages or benefits may also beachieved.

Some embodiments described herein are in the context of Back End of theLine (BEOL) processing. Other processes and structures within the scopeof other embodiments may be performed in other contexts, such as inMiddle End of the Line (MEOL) processing and other contexts. Variousmodifications are discussed with respect to disclosed embodiments;however, other modifications may be made to disclosed embodiments whileremaining within the scope of the subject matter. A person havingordinary skill in the art will readily understand other modificationsthat may be made that are contemplated within the scope of otherembodiments. Although method embodiments may be described in aparticular order, various other method embodiments may be performed inany logical order and may include fewer or more steps than what isdescribed herein.

FIGS. 1 through 6 illustrate cross-sectional views of respectiveintermediate structures during an example method for forming aconductive feature in accordance with some embodiments. FIG. 1illustrates a first dielectric layer 22 over a semiconductor substrate20. The semiconductor substrate 20 may be or include a bulksemiconductor, a semiconductor-on-insulator (SOI) substrate, or thelike, which may be doped (e.g., with a p-type or an n-type dopant) orundoped. In some embodiments, the semiconductor material of thesemiconductor substrate 20 may include elemental semiconductor likesilicon (Si) and germanium (Ge); a compound semiconductor; an alloysemiconductor; or a combination thereof.

Various devices may be on the semiconductor substrate 20. For example,the semiconductor substrate 20 may include Field Effect Transistors(FETs), such as Fin FETs (FinFETs), planar FETs, vertical gate allaround FETs (VGAA FETs), or the like; diodes; capacitors; inductors; andother devices. Devices may be formed wholly within the semiconductorsubstrate 20, in a portion of the semiconductor substrate 20 and aportion of one or more overlying layers, and/or wholly in one or moreoverlying layers, for example. Processing described herein may be usedto form and/or to interconnect the devices to form an integratedcircuit. The integrated circuit can be any circuit, such as for anApplication Specific Integrated Circuit (ASIC), a processor, memory, orother circuit.

The first dielectric layer 22 is above the semiconductor substrate 20.The first dielectric layer 22 may be directly on the semiconductorsubstrate 20, or any number of other layers may be disposed between thefirst dielectric layer 22 and the semiconductor substrate 20. Forexample, the first dielectric layer 22 may be or include an Inter-MetalDielectric (IMD). The first dielectric layer 22, for example, may be orcomprise a low-k dielectric having a k-value less than about 4.0, suchas about 2.0 or even less. In some examples, the first dielectric layer22 comprises silicon oxide, phosphosilicate glass (PSG),borophosphosilicate glass (BPSG), fluorosilicate glass (FSG),SiO_(x)C_(y), silicon carbon material, a compound thereof, a compositethereof, or a combination thereof.

A conductive feature 24 is in and/or through the first dielectric layer22. The conductive feature 24 may be or include a conductive line and/ora conductive via. For example, the first dielectric layer 22 may be anIMD, and the conductive feature 24 may include a conductive line and/ora conductive via (collectively or individually, “interconnectstructure”). The interconnect structure may be formed by forming anopening and/or recess through and/or in the IMD, for example, using adamascene process. The interconnect structure can include, for example,a barrier layer and/or a surface modification layer (as describedherein) along sidewalls of the first dielectric layer 22 and a metalfill material (e.g., copper, etc.).

A first etch stop sub-layer 26 is over the first dielectric layer 22 andthe conductive feature 24, and a second etch stop sub-layer 28 is overthe first etch stop sub-layer 26. An etch stop layer can provide amechanism to stop an etch process when forming, e.g., conductive vias.An etch stop layer may be formed of a dielectric material having adifferent etch selectivity from adjacent layers or components. The firstetch stop sub-layer 26 is deposited on the top surfaces of the firstdielectric layer 22 and the conductive feature 24, and the second etchstop sub-layer 28 is deposited on the top surface of the first etch stopsub-layer 26. The first etch stop sub-layer 26 and the second etch stopsub-layer 28 are formed of different materials such that each layer hasa different etch selectivity for etch stopping purposes. The first etchstop sub-layer 26 and the second etch stop sub-layer 28 may eachcomprise or be silicon nitride, silicon oxynitride, silicon oxide,silicon carbon nitride, carbon nitride, the like, or a combinationthereof, and may be deposited by chemical vapor deposition (CVD), plasmaenhanced CVD (PECVD), atomic layer deposition (ALD), or anotherdeposition technique. For example, the first etch stop sub-layer 26 canbe silicon oxynitride, and the second etch stop sub-layer 28 can besilicon nitride. A thickness of the first etch stop sub-layer 26 can bein a range from about 1 nm to about 10 nm, and a thickness of the secondetch stop sub-layer 28 can be in a range from about 1 nm to about 10 nm.

A second dielectric layer 30 is over the second etch stop sub-layer 28.For example, the second dielectric layer 30 may be or include an IMD.The second dielectric layer 30 is deposited on the top surface of thesecond etch stop sub-layer 28. The second dielectric layer 30, forexample, may be or comprise a low-k dielectric having a k-value lessthan about 4.0, such as in a range from about 2.0 to about 3.0, or evenless. In some examples, the second dielectric layer 30 comprises or issilicon oxide, a silicon oxide-like material, PSG, BPSG, FSG,SiO_(x)C_(y), a silicon carbon material, a compound thereof, a compositethereof, or a combination thereof. The second dielectric layer 30 may bedeposited using CVD, such as PECVD or Flowable CVD (FCVD); spin-oncoating; or another deposition technique. In some examples, a ChemicalMechanical Planarization (CMP) or another planarization process may beperformed to planarize the top surface of second dielectric layer 30. Athickness of the second dielectric layer 30 can be in a range from about20 nm to about 100 nm.

A hardmask 32 is over the second dielectric layer 30. The hardmask 32can be implemented for subsequently etching an opening through thesecond dielectric layer 30. The hardmask 32 may comprise or be siliconoxide formed by tetraethoxysilane (TEOS), silicon nitride, siliconcarbon nitride, carbon nitride, titanium nitride, the like, or acombination thereof, and may be deposited by CVD, physical vapordeposition (PVD), or another deposition technique. A thickness of thehardmask 32 can be in a range from about 8 nm to about 50 nm.

The configuration of FIG. 1 is an example to illustrate aspects herein.In other examples, various other layers may be included, omitted, and/ormodified. A person having ordinary skill in the art will readilyunderstand various modifications that may be made.

FIG. 2 illustrates the formation of an opening 34 in and/or through thehardmask 32, second dielectric layer 30, second etch stop sub-layer 28,and first etch stop sub-layer 26 to the conductive feature 24. Theopening 34 can be or include a via opening, a trench, and/or the like.The opening 34 can be formed using photolithography and etch processes,such as in a damascene process. The etch process may include a reactiveion etch (RIE) or another etch process. The etch process may beanisotropic.

More specifically, in some examples, the opening 34 is formed using anRIE process, a wet clean process, a baking process, and a post-cleanprocess. In some examples, the RIE process is implemented to etchthrough the second dielectric layer 30. In some examples, the RIEprocess etches through the second dielectric layer 30 and stops at thesecond etch stop sub-layer 28. The RIE process can implement an etchantgas comprising a carbon fluoride (C_(x)F_(y)) gas and/or another gas.The RIE process can further use a carrier gas, such as argon (Ar) or thelike. A flow rate of the etchant gas can be in a range from about 20sccm to about 500 sccm, and a flow rate of the carrier gas can be in arange from about 20 sccm to about 500 sccm. A ratio of the flow rate ofthe etchant gas to the flow rate of the carrier gas can be in a rangefrom about 1 to about 25. A pressure of the RIE process can be in arange from about 1 mTorr to about 100 mTorr. A temperature of the RIEprocess can be in a range from about 0° C. to about 100° C. The RIEprocess can implement an inductively coupled plasma (ICP). The plasmagenerator of the RIE process can have a power in a range from about 50 Wto about 1800 W and at frequency in a range from about 2 MHz to about 80MHz, such as 13.56 MHz. A substrate bias of the RIE process can be in arange from about 50 V to about 1.8 kV. Other examples can implementother etch processes and/or parameters. The parameters can be tuned tobe within or outside of the various ranges described above based ondesign considerations such as materials implemented and/or profile ofthe opening 34.

Thereafter, a wet clean process is implemented to remove residue fromthe RIE process and break through the second etch stop sub-layer 28 andthe first etch stop sub-layer 26 to expose the conductive feature 24. Insome examples, the wet clean process implements a solution comprising afluoride acid and an organic solvent. For example, the solution cancomprise hydrofluoric (HF) acid and a glycol. The solution can have aratio of the fluoride acid to the organic solvent in a range from about1:10 (by volume) to about 1:5000 (by volume). The solution may be at atemperature in a range from about 20° C. to about 60° C., and may beapplied for a duration in a range from about 0.1 minutes to about 5minutes. The solution can be applied by spin-on, immersion, or any othertechnique.

After the wet clean process, a mild bake process can be performed todrive moisture out of the intermediate structure of FIG. 2 . The mildbake process can be performed at a temperature in a range from about200° C. to about 400° C., such as about 300° C., for a duration in arange from about 5 minutes to about 10 minutes.

In some examples, as a result of the etch and wet clean processes, anoxide can be formed on the exposed top surface of the conductive feature24, and the post-clean process can be performed to remove the oxide onthe conductive feature 24. The post-clean process can include an ionbombardment, a plasma treatment with a forming gas, and/or rinse incitric acid, for example.

The sidewalls of the opening 34 are illustrated as being vertical. Inother examples, sidewalls of the opening 34 may taper together in adirection toward or away from the bottom of the opening 34. For example,the opening 34 may have a positive taper profile or a reentrant profile.

As illustrated, the opening 34 has a width 34 W and a depth 34D. Thewidth 34 W is in a plane of the top surface of the second dielectriclayer 30. The depth 34D is from the top surface of the second dielectriclayer 30 to the exposed surface of the conductive feature 24. The width34 W can be in a range from about 5 nm to about 40 nm, and the depth 34Dcan be in a range from about 30 nm to about 100 nm. An aspect ratio ofthe depth 34D to the width 34 W can be in a range from about 3 to about6. A person having ordinary skill in the art will readily understandthat various dimensions, such as thicknesses of layers and depth andwidth of the opening 34, can vary depending on the technology node ofthe process and layer of the structure being formed. For example,conductive features in lower IMD layers generally have a smaller widththan conductive features in upper IMD layers.

FIG. 3 illustrates the formation of a surface modification layer 40 inthe opening 34 along the sidewalls of the second dielectric layer 30 andon the top surface of the hardmask 32. The surface modification layer40, in some examples, is a self-aligned monolayer (SAM) that repairsdamage to surfaces of the second dielectric layer 30. In some examples,surfaces of the second dielectric layer 30 can be damaged during plasmaprocesses, such as an RIE process that forms the opening 34. Forexample, the plasma process can deplete the surface of carbon. Further,some processes, such as a wet clean process, can terminate surfaces ofthe second dielectric layer 30 with hydroxide (—OH) groups. Individuallyand/or together, the depletion of carbon and the termination withhydroxide groups can cause the dielectric value (k-value) of the seconddielectric layer 30 to increase. The surface modification layer 40 canremove the hydroxide groups and replenish carbon at the surfaces of thesecond dielectric layer 30 to repair the second dielectric layer 30. Thesurface modification layer 40 is a dielectric material and is free frommetal, in some embodiments.

In some examples, the surface modification layer 40 includes a monolayerof a molecule comprising phosphorous and one or more organic functionalgroups. In some examples, the surface modification layer 40 is formed byexposing the surfaces of the second dielectric layer 30 to a phosphoricacid derivative. The phosphoric acid derivative has the general chemicalstructure of an oxygen atom double bonded to a phosphorous atom, ahydroxide group single bonded to the phosphorous atom, and two organicfunctional groups each single bonded to the phosphorous atom. In someexamples, the organic functional groups are or include functional groupsof alky, alkoxy, amine, ester, phenyl, the like, or a combinationthereof. In some examples, the phosphoric acid derivative is or includesDi-(2-ethylhexyl)phosphoric acid, dihexylphosphoric acid, ethylhexadecyl phosphate, n-Butyl-octyl-hydrogenphosphate,diisoamylphosphoric acid, ethyl octyl phosphate, the like, or acombination thereof.

In some examples, the phosphoric acid derivative is exposed to thesurfaces of the second dielectric layer 30 using a wet process or a dryprocess. In some examples, a wet process is implemented. The wet processcan include using a solution comprising the phosphoric acid derivativeand an organic solvent. Example organic solvents include ethyleneglycol, diethanolglycol (DEG), glycol ethers, the like, or a combinationthereof. The solution can include the phosphoric acid derivative andorganic solvent at a ratio in a range from about 1:100000 (phosphoricacid derivative:organic solvent) (by volume) to about 1:100 (phosphoricacid derivative:organic solvent) (by volume). The wet process, in someexamples, includes using a spin coating process to apply the solution tothe surfaces of the second dielectric layer 30. The solution may be at atemperature in a range from about 20° C. to about 60° C., and may beapplied for a duration in a range from about 0.1 minutes to about 10minutes. If too low of an amount or concentration of the phosphoric acidderivative is implemented (e.g., if a ratio of the phosphoric acidderivative to solvent is too low and/or the duration is too short), thephosphoric acid derivative may not react sufficiently to form thesurface modification layer 40. After the solution is applied, a rinseprocess may be performed to remove any remaining solution andby-products. The rinse process can include rinsing with a mixture ofdeionized water and isopropyl alcohol (IPA) followed by rinsing with IPAfor drying.

In some examples, a dry process is implemented. The dry process caninclude flowing one or more gases over the surfaces of the seconddielectric layer 30. The one or more gases include a phosphoric acidderivative, and can further include a carrier gas, such as nitrogen(N₂), argon (Ar), or the like. The dry process can be performed withoutusing a plasma. The phosphoric acid derivative gas can be flowed at aflow rate in a range from about 1 sccm to about 100 sccm, and a carriergas, if used, can be flowed at a flow rate in a range from about 50 sccmto about 500 sccm. A ratio of the flow rate of the phosphoric acidderivative gas to the flow rate of the carrier gas can be in a rangefrom about 1:50 to about 1:500. A pressure of the ambient of the dryprocess can be in a range from about 10 mTorr to about 1 Torr, and atemperature of the dry process can be in a range from about 20° C. toabout 100° C. A duration of the dry process can be in a range from about0.1 minutes to about 10 minutes. If too low of an amount orconcentration of the phosphoric acid derivative gas is implemented(e.g., if a flow rate is too low and/or the duration is too short), thephosphoric acid derivative gas may not react sufficiently to form thesurface modification layer 40. After the exposure, a purge process canbe implemented, such as by flowing an inert gas like argon (Ar), toremove any remaining phosphoric acid derivative gas and by-products.

FIGS. 7A, 7B, and 7C illustrate a mechanism for forming the surfacemodification layer 40 in accordance with some embodiments. FIG. 7Aillustrates a surface of the second dielectric layer 30, which is formedas described above. The surface includes silicon oxide that isterminated with hydroxide groups, which can be the result of damage tothe second dielectric layer 30, as described above. FIG. 7B illustratesthe general chemical structure of a phosphoric acid derivative. Thephosphoric acid derivative includes a phosphorous atom (i) double bondedto an oxygen atom (O), (ii) single bonded to a hydroxide group (—OH),(iii) single bonded to a first organic functional group (R1), and (iv)single bonded to a second organic functional group (R2). The phosphoricacid derivative of FIG. 7B is exposed to the surface of the seconddielectric layer 30 of FIG. 7A using a wet or dry process as describedabove. The phosphoric acid derivative reacts with the surface of thesecond dielectric layer 30 to form the surface modification layer 40.The reaction results in a bridging oxygen atom that forms bonds withsilicon (Si) and the phosphorous of the phosphoric acid derivative andresults in a by-product of water vapor (H₂O). The surface modificationlayer 40 that is formed includes a monolayer of molecules, where eachmolecule includes phosphorous, oxygen, the first organic functionalgroups R1, and the second organic functional groups R2. By-products andresidual fluids can be removed by the rinsing or purging describedabove.

Referring back to FIG. 3 , the surface modification layer 40 has athickness 40T. The thickness 40T is in a range from about 1 nm to about2 nm in some examples. With the reactions that occur as describedpreviously, the formation of the surface modification layer 40 may beself-limiting since reactions can saturate when the reaction sites onthe surfaces of the second dielectric layer 30 react with the phosphoricacid derivative.

Further, in some examples, the surface modification layer 40 isselectively formed on the surfaces of the second dielectric layer 30 butnot on an exposed surface of the conductive feature 24. Additionally, insome examples, the surface modification layer 40 may not be formed onsurfaces of the first etch stop sub-layer 26 and the second etch stopsub-layer 28. As illustrated in FIGS. 7A through 7C, a chemical reactionbetween the surface of the second dielectric layer 30 and the phosphoricacid derivative forms the surface modification layer 40. Since thesurfaces of the conductive feature 24, first etch stop sub-layer 26, andsecond etch stop sub-layer 28 are materials different from the seconddielectric layer 30, and hence, have a different chemical structure fromthe second dielectric layer 30, those surfaces may not react with thephosphoric acid derivative, and hence, a surface modification layer 40may not be formed on those surfaces in some examples. For example, theremoval of an oxide from the exposed surface of the conductive feature24 after the opening 34 is formed, as described above, can result in ametallic surface without oxygen being on the exposed surface of theconductive feature 24. This metallic surface may not be able to reactwith the phosphoric acid derivative, and hence, a surface modificationlayer 40 may not be formed on the metallic surface in some examples.

FIG. 4 illustrates the formation of a conductive fill material 42 on thesurface modification layer 40, which fills the opening 34. Theconductive fill material 42 can be or include a metal fill, such ascopper, tungsten, cobalt, aluminum, ruthenium, the like, or acombination thereof. The conductive fill material 42 can be deposited byany acceptable deposition process, such as PVD, plating (e.g.,electroless plating), CVD, the like, or a combination thereof.

FIG. 5 illustrates the removal of the hardmask 32, the surfacemodification layer 40 formed on the hardmask 32, and excess conductivefill material 42 to form a conductive feature (comprising the conductivefill material 42) in the second dielectric layer 30. The hardmask 32,the surface modification layer 40 formed on the hardmask 32, and excessconductive fill material 42 can be removed using a planarizationprocess, such as a CMP, which can form upper surfaces of the conductivefill material 42, surface modification layer 40, and second dielectriclayer 30 to be level. A conductive feature, such as in a damasceneinterconnect structure, can be formed, as illustrated in FIG. 5 . Morespecifically, the conductive feature (e.g., conductive fill material 42)contacts the surface modification layer 40 on sidewalls of the seconddielectric layer 30, contacts the top surface of the conductive feature24, and, if the surface modification layer 40 is not formed on thesidewalls of the first etch stop sub-layer 26 and second etch stopsub-layer 28, contacts the sidewalls of the first etch stop sub-layer 26and second etch stop sub-layer 28. Further, the surface modificationlayer 40 is disposed between the conductive feature (e.g., conductivefill material 42) and the second dielectric layer 30 and is laterallyaround the conductive feature (e.g., conductive fill material 42).

FIG. 6 illustrates the formation of a third etch stop sub-layer 50, afourth etch stop sub-layer 52, a third dielectric layer 54, and aconductive feature 56. The third etch stop sub-layer 50 is formed overthe second dielectric layer 30, the surface modification layer 40, andthe conductive feature (comprising the conductive fill material 42). Thefourth etch stop sub-layer 52 is formed over the third etch stopsub-layer 50. The third dielectric layer 54 is formed over the fourthetch stop sub-layer 52. The third etch stop sub-layer 50, the fourthetch stop sub-layer 52, and the third dielectric layer 54 can be formedas described above with respect to the first etch stop sub-layer 26, thesecond etch stop sub-layer 28, and the second dielectric layer 30,respectively, with reference to FIG. 1 . In other examples, differentlayers may be formed, and/or different processes may be implemented.

An opening may be formed through the third dielectric layer 54, thefourth etch stop sub-layer 52, and the third etch stop sub-layer 50 toexpose the conductive feature (comprising the conductive fill material42) in the second dielectric layer 30. The conductive feature 56 maythen be formed in the opening and contacting the conductive feature inthe second dielectric layer 30. The opening and the conductive feature56 may be formed as described above with respect to the opening 34 andconductive feature (comprising the conductive fill material 42),respectively, with reference to FIGS. 2 through 5 . A surfacemodification layer may or may not be formed along sidewalls of theopening. A barrier layer (e.g., metal-nitride layer) may or may not beformed in the opening. In other examples, different materials and/orlayers may be formed, and/or different processes may be implemented.

In some embodiments, the processing described above can implement adamascene process. A damascene process can be implemented to form aconductive line in a single damascene process, for example, or to form aconductive line with a via in a dual damascene process, for example.Some examples described herein may be implemented in a single damasceneprocess or a dual damascene process. In some examples, various sidewallsand surfaces described herein may be of an opening in a dielectric layerfor a conductive line and/or of an opening in a dielectric layer for aconductive line and a via. Surface modification layers may beimplemented in a single damascene process or a dual damascene processand may be formed on the various surfaces formed by such processing.Other examples can be implemented in other processes.

In some examples, a barrier layer (e.g., a metal-nitride layer) is notconformally deposited in the opening 34 and does not form part of theconductive feature that includes the conductive fill material 42. Thesurface modification layer 40 may have barrier characteristics that canprevent extrusion or diffusion of the conductive fill material 42 intothe second dielectric layer 30. For example, the more linear the organicfunctional groups that are included in the phosphoric acid derivativeare, the more dense the surface modification layer 40 can be. A largerdensity of the surface modification layer 40 can contribute to thesurface modification layer 40 having barrier characteristics. In someexamples, a density of the surface modification layer 40 that hasbarrier characteristics can be in a range from 1×10¹⁵ atoms/cm² to about1×10²² atoms/cm². Hence, a separate barrier layer can be omitted in someexamples, although in other examples, a barrier layer can be included inaddition to the surface modification layer 40. For example, in someexamples, a barrier layer (such as of tantalum nitride or titaniumnitride) is conformally deposited on the surface modification layer 40before the conductive fill material 42 is deposited.

If a separate barrier layer is not included, resistance of theconductive feature that is formed can be reduced. Separate barrierlayers can be formed of a metal-nitride, such as tantalum nitride ortitanium nitride, and can be formed with a greater thickness than thesurface modification layer 40. A conformal barrier layer can be formedalong all surfaces of the opening 34, including a top surface of theconductive feature 24. Hence, such a conformal barrier layer would beformed disposed between the conductive feature 24 and the conductivefill material 42. When the conformal barrier layer is a metal-nitride(which can be a higher resistance material), a resistance of theconductive features can be increased due to the presence of theconformal nitride barrier layer between the conductive feature 24 andthe conductive fill material 42. With the surface modification layer 40being implemented without a separate barrier layer, no metal-nitridelayer would be disposed between the conductive feature 24 and theconductive fill material 42, and hence, a resistance can be decreased.Additionally, a thickness of the surface modification layer 40 can beless than the thickness of a conformal barrier layer. Hence, across-sectional area of the conductive fill material 42 perpendicular tothe flow of electrical current (e.g., parallel to the top surface of theconductive feature 24) can be greater when the surface modificationlayer 40 is implemented compared to when a barrier layer is implemented,assuming a same opening size. The greater cross-sectional area canresult in a reduced resistance of the conductive feature that includesthe conductive fill material 42. Further, with the surface modificationlayer 40 being implemented and not a separate barrier layer, and moreparticularly, with the surface modification layer 40 being a monolayer,a process window for forming the conductive feature that includes theconductive fill material 42 can be increased.

The surface modification layer 40, in some examples, is formed by aself-limiting reaction with the exposed surfaces of the seconddielectric layer 30. Hence, in those examples, a monolayer of a giventhickness can be formed regardless of duration of the exposure after theself-limiting reactions saturate the exposed surfaces. By saturating theexposed surfaces of the second dielectric layer 30, discontinuities inthe surface modification layer 40 can be reduced (compared to otherlayers) or avoided. By reducing or avoiding discontinuities, a timedependent dielectric breakdown (TDDB) failure can be increased. Forexample, a TDDB failure of a structure formed without a surfacemodification layer was 14 years in some testing, while a structureformed with a surface modification layer was 370 years in some testing.

As described above, the surface modification layer 40 can repair damageto the second dielectric layer 30. Particularly, in some examples, thesecond dielectric layer 30 is a low-k dielectric of silicon oxycarbide(SiO_(x)C_(y)). The low-k dielectric, when exposed to a plasma, can havecarbon depletion, which can increase the k-value of the dielectric.Further, processes performed on the low-k dielectric can result inhydroxide (—OH) groups terminating surfaces of the dielectric, which canfurther increase the k-value of the dielectric. As illustrated by FIGS.7A through 7C, the formation of the surface modification layer 40removes the hydroxide groups from the surfaces of the low-k dielectricto recover some of the k-value of the dielectric. Further, the organicfunctional groups that are included in the surface modification layer 40can replenish carbon at the surfaces where the surface modificationlayer 40 is formed to thereby recover some of the k-value of thedielectric.

Accordingly, some embodiments can achieve reduced resistance, reducedextrusion or diffusion of conductive material, increased TDDB failuretimes, and recovered k-values. These can, together and/or individually,increase passing rates of wafer acceptance testing (WAT) and increaseyield. Some embodiments may be implemented at any technology node, andmore particularly, may be implemented at a 10 nm technology node andsmaller.

An embodiment is a structure. The structure includes a dielectric layerover a substrate, a surface modification layer, and a conductivefeature. The dielectric layer has a sidewall. The surface modificationlayer is along the sidewall, and the surface modification layer includesphosphorous and carbon. The conductive feature is along the surfacemodification layer.

Another embodiment is a structure. The structure includes a firstdielectric layer, a first conductive feature, a second dielectric layer,a surface modification layer, and a second conductive feature. The firstdielectric layer is over a substrate. The first conductive feature isdisposed in the first dielectric layer. The second dielectric layer isover the first dielectric layer, and the second dielectric layer hassidewalls. The surface modification layer is along the sidewalls of thesecond dielectric layer, and the surface modification layer includesphosphorous and carbon. The second conductive feature is disposedbetween the sidewalls of the second dielectric layer, and the secondconductive feature contacts the first conductive feature.

A further embodiment is a method for semiconductor processing. Anopening is etched through a dielectric layer. The dielectric layer isover a substrate. Surfaces of the dielectric layer that define theopening are exposed to a phosphoric acid derivative. A conductive fillmaterial is deposited in the opening.

The foregoing outlines features of several embodiments so that thoseskilled in the art may better understand the aspects of the presentdisclosure. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions, andalterations herein without departing from the spirit and scope of thepresent disclosure.

What is claimed is:
 1. A method of manufacturing a semiconductor device,the method comprising: depositing a dielectric layer over a conductiveregion over a semiconductor substrate; forming an opening through thedielectric layer to expose the conductive region; treating exposedportions of the dielectric layer with a self-limiting reaction to form amonolayer of material, wherein the self-limiting reaction deposits aphosphoric acid derivative material as part of the monolayer ofmaterial; and depositing conductive material within the opening.
 2. Themethod of claim 1, wherein the treating the exposed portions of thedielectric layer is performed at least in part with a wet process. 3.The method of claim 2, wherein the wet process comprises applying asolution, the solution comprising a phosphoric acid derivative and anorganic solvent.
 4. The method of claim 3, wherein the organic solventcomprises ethylene glycol.
 5. The method of claim 3, wherein thephosphoric acid derivative comprises Di-(2-ethylhexyl)phosphoric acid ordihexylphosphoric acid.
 6. The method of claim 3, wherein the phosphoricacid derivative comprises ethyl hexadecyl phosphate orn-Butyl-octyl-hydrogenphosphate.
 7. A method of manufacturing asemiconductor device, the method comprising: forming an opening througha dielectric layer to expose an underlying conductive region;replenishing carbon at a surface of the dielectric layer by applying aphosphoric acid derivative to the surface of the dielectric layer; andfilling the opening with a conductive material.
 8. The method of claim7, wherein the replenishing the carbon is performed at least in partwith a dry process.
 9. The method of claim 8, wherein the dry processflows a phosphoric acid derivative gas over the surface of thedielectric layer.
 10. The method of claim 9, wherein the phosphoric acidderivative gas comprises diisoamylphosphoric acid or ethyl octylphosphate.
 11. The method of claim 9, wherein the phosphoric acidderivative gas is flowed at a flow rate of between 1 sccm and wo sccm.12. The method of claim 11, wherein the dry process is performed at apressure of between 10 mTorr and 1 Torr.
 13. The method of claim 12,wherein the dry process is performed at a temperature of between 20° C.and wo ° C.
 14. The method of claim 8, wherein the dry process isperformed without using a plasma.
 15. A method of manufacturing asemiconductor device, the method comprising: forming an opening througha dielectric layer to expose an underlying conductive region; andreplacing OH groups on a surface of the dielectric layer with amonolayer comprising phosphoric acid derivative molecules, the monolayerhaving a thickness no thicker than a length of one of the phosphoricacid derivative molecules.
 16. The method of claim 15, wherein thereplacing the OH groups on the surface of the dielectric layer comprisesapplying a solution, the solution comprising the phosphoric acidderivative molecules.
 17. The method of claim 15, wherein the replacingthe OH groups on the surface of the dielectric layer comprising flowinga gas over the surface of the dielectric layer.
 18. The method of claim17, wherein the flowing the gas over the surface of the dielectric layeris performed without a plasma.
 19. The method of claim 15, wherein theopening has an aspect ratio in a range from 3 to
 6. 20. The method ofclaim 15, wherein the replacing the OH groups on the surface of thedielectric layer is performed as part of a middle end of line process.